Sulfate derivatives of polyglycol compounds

ABSTRACT

New polyglycol compounds are provided which are amphoteric derivatives of polyglycol compounds containing (a) an aliphatic hydrocarbon residue containing 12 to 24 carbon atoms, which is bound to nitrogen, and (b) -(CH2-CH2-O-)k groups bound to nitrogen, where k is a whole positive number, the molecule containing in all 4 to 12 -CH2-CH2-O- groups, which polyglycol compounds are, on one hand, quaternated with organic halogen compounds and esterified with at least dibasic oxygen acids with formation of acid ester groups. The compounds of the present invention are especially useful as dyeing auxiliaries, and more particularly, as levelling agents for the dyeing of wool.

United States Patent Berger et a1.

1 1 SULFATE DERIVATIVES OF POLYGLYCOL COMPOUNDS [75] Inventors: AlfredBerger; Heinz Abel, both of Reinach. Basel. Switzerland Related US.Application Data [63] Continuation of Set. No. 833.866. June 3. 1969.abandoned. which is a continuation of Ser. No. 533.774. March 14. 1966.abandoned.

[30] Foreign Application Priority Data Mar. 18. 1965 Switzerland 3812/65.1u1 29. 1965 Switzerland 10691/65 {52] US. Cl 260/458; 260/481 R;260/561 A; 260/5676 M; 260/5676 P; 8/1 P; 8/1 S [51] Int. Cl. C07C141/02 [58] Field of Search 260/458, 481 R [56] References Cited FOREIGNPATENTS OR APPLICATIONS 355.457 8/1961 Switzerland 260/458 902.3748/1962 United Kingdom 260/458 14 1 Nov. 11, 1975 852.548 10/1960 UnitedKingdom 260/458 888.661 1/1962 United Kingdom 260/458 465.200 4/1937United Kingdom 260/458 310.412 8/1963 Japan 260/458 PrimaryE.\'uminerBernard Helfin Assistant Eruminew-Nicky Chan Allol'lle).Agent. or FirmJoseph G. Kolodny: Edward McC. Roberts; Prabodh l. Almaula[57] ABSTRACT New polyglycol compounds are provided which are amphotericderivatives of polyglycol compounds containing (a) an aliphatichydrocarbon residue containing 12 to 24 carbon atoms. which is bound tonitrogen. and (b) -(CH- ]-CHg-O-)k groups bound to nitrogen. where k isa whole positive number. the molecule containing in all 4 to 12 -CH- -CH-O- groups. which polyglycol compounds are. on one hand. quaternatedwith organic halogen compounds and esterified with at least dibasicoxygen acids with formation of acid ester groups.

The compounds of the present invention are especially useful as dyeingauxiliaries. and more particularly. as levelling agents for the dyeingof wool.

6 Claims. N0 Drawings (CH-Cl-l 'O- -,H This is a continuation ofapplication Ser. N t t 1 833,866, filed on June 3, 1969 now abandoned,which is a streamlined continuation of application Ser. No. 533,774,filed Mar. 14, 1966, now abandoned.

The present invention provides new polyglycol compounds suitable for useas dyeing auxiliaries. These compounds are amphoteric derivatives ofpolyglycol compounds containing V a. an aliphatic hydrocarbon residuecontaining 12 to 24 carbon atoms, which is bound tonitrogen, and

b. -(CH -CH -O-) groups bound to nitrogen, where k is a whole positivenumber, the molecule containing in all 4 to 12 CH -CH O- groups, whichpolyglycol compounds are, on one hand, quaternated with organic halogencompounds and, on the other hand, esterified with at least dibasicoxygen acids with formation of acid ester groups. These new amphotericpolyglycol compounds are advantageously 0b- (Ill) N tcH, cH, 0+,, tainedwhen glycol compounds which contain \CHPCHPOkH aan aliphatic hydrocarbonresidue containing 12 to 24 carbon atoms, whichis bound to nitrogen,fi(-CH -CH -O) -H groups [where k is a whole positive number] bound tonitrogen, the molecule containing a total of 4 to 12 -CH,-CH -O-groups,and yexclusively tertiary amino groups arequaternated,

on one hand, with organic halogen compounds 30 and, on the other hand,est'erified onatleast one -CH -CH -OH group to forman acid ester derivedfrom an at least dibasic oxygen acid.

The polyglycol compounds contain advantageously 6 to 9 -CH -CH -O-groups(ethenoxy groups), and also saturated or unsaturated aliphatichydrocarbonresidues, which may be branched or preferably are linear; andcontain advantageously 16 to 18 carbon atoms; The quaternation andesterification may be'carried out in either order. The -CH -CH -OHgroups'are esterified with functional derivativesof dibasic orpolybasic'oxy-' 1 gen acids under conditions such that at least one acid(w) 1 P P Hr ester group, preferably in the form of an alkali metal 1 2salt orammonium or amine salt thereof, is introduced.

A preferred sub-group of the new polyglycol deriva 45 tives, which isdistinguished by their particularly easy 1 accessibility, are thequaternary compounds derived Where R represents a Preferably linealaliphatic y from organic, halogen-containing quaternating agents carbonresidue n in g 12 t0 p f rably 16 t0 and f om a id esters f th f l 18,carbon atoms, n 2 or 3, and p, q and r are whole (wjhereR, n,.rn,,p, qandrha ve the. same meanings as in formula l yare. in eithe rno'rder ofsuccession, on one and, i on the, other hand, esterified on at least one-Cl-l Cl-l -,OH, group to form an, acid ester derived from an at leastdibasicoxygen acid, andthe reaction conditions are advantageously chosenso that the acid ester groups are introduced in the form oftheir alkalimetal or ammoniun or amine salts.

. Suitable starting materials for themanufacture of the new polyglycolcompounds of this invention, which contain both acid ester groups andquaternary ammoniumgroups are above all basic polyglycol ethers of theformula where represents a preferably linear aliphatic hydrocarbon residue contairiing [2 to 24, preferably 16 to 20, carbon atoms, and p andq are whole numbers, the sum (p-l-q) being from 4 to 12, preferably from6 to 9. compounds of the formula (III) there may be mentioned, forexample; The reaction product of 1 mol of dodecylamine withabout 6 molsof ethylene oxide, or of l rnol ofoleylamine with 6, or 12 mols ofethylene oxide, or ofl nioliof palmityl-, stearylarachidylamine orbehenylamine with 4 8 or 12 rnols of ethylene oxide, or reactionproducts of mixtures of such amines with 4 to, 12 mols of ethylene oxideper mol of amine mixturel Furthermore, there are specially suitablepolyglycol 40 compounds of the formula in which R represents apreferably linear aliphatic hydrocarbon residue containing 12 to 24carbon atoms, X i

the residue formed when a hydroxyl group is eliminated numbers, the sum(p-l-q+r) being from 4 to l2, preferafrom a polybasic organic orinorganic oxygen acid,; bly from 6 to 9.

which residue is advantageously in the form of an alkali As compounds.of the formula (IV) there may be metal or ammonium or amine saltthereof; m =0 or 1; mentioned, for example: The reaction product of mon2 or 3, s is a whole number from at least 1 to at mostnoalkyl-propylenediamine, whose alkyl radical corre- 2+m, and p, q, andr are whole numbers, the sum (p sponds to the residue of tallow fattyacid, with 8 mols of q r) being from 4 to 12, preferably from 6 to 9.ethylenev oxide and the. reaction product of monoalkyl- The amphotericpolyglycol compounds of the forpropylenediamine, whose alkyl radical islinear and mula (I) are obtained when a nitrogen-containing polycontainsl6lto 18 carbon atoms, with 6 mols of ethylglycol compound of theformula ene oxide.

hand, quaternated with organic halogen compounds Both the quaternationand the esterification are advantageouslyzperfiormed in the knownmanner. No intermediate isolation isnededz- W1 The q uaternatio n may beachieve d l with a conventional halogen-containing alkylating oraralkylating agent, such as ethylbromide or benzylchloride though prefried c'ihz'itfriatiiigagent's are qizhloro'acetaifii de' a r-lavaeeiflaiaiiyamt; mbh'ydiing e siem a's lveiingfagent's i "a' 'iilgnitroger'iepu npr ci'all y ta/601; with @661 d estuffs bbritaifiiiig aclimparting solubility in water, especially with re dyestuffsand l :i'ifietai i dyestuffs: iWhil true that different types ofpolyglycofethei"derivatives containing amino groups have already beenproposed for thispurpose; for 'example basic p plyglycol coin' poundsobtained by adding, rormsmhee; 6 to 30 mols of ethylene oxide on tohigh-molecular primary aliphatic monoamines, siich as'oleylamine, theseknown levelling agents which are generally used in an amount from about:0.1 .to SI percent by weight, advantage'ously 0.5 to 3 percent-by weightrefer re'd to the weight of the material to be dyed aresnot suitable forgeneral use in connection with wool. Whereas the use of the levellingagents of the indicated type gives in ideal apparatus very leveldyeings, there generally intervene different disturbing factors when theleast advantageous apparatus is used, thus in dyeing woollen tops,especially when 1 dyeing wool yarn in apparatus by the so-calledsuspeii- 1 sion system with wool dyestuffs in the presence of theaforesaid levelling agents, Inter alia, in addition to the irksomeappearance of visible scum, air bubbles are very. tenaciously;retaihedfori the fibre surface; thisldist-i turbs the uniformpenetration of the materialwtoi be! dyed and causes a tendency of :therma'terialto :rise to thezsurface ofthehbathwThis' istparticularl'ynoticeable ass-a deformation :of the material-when dyeingcrosswoundwbobbinsn if. .uf}, u i was; 11 w Furthermore, the knownllevellingaagentstincreasethe adhesion betweenufibres a'nd fibres sotth'at at moretora lessrextensiverstickingxtogethenofethe yarns occurs,which causes the formation of channels in the material:

' costlytm and results in its irregular dyeing. Furthermore, the wn lvellingi g -t h ve-t d sadv nt g u PI P- erty that dehydrationcauses-add'ucts-from dyestuff and levelling agent on heating, generallybelow the boiling temper tu e 1orse t e ut zthefot mrq dr p ts 1(t sor-ia edtturbidityt Pdin lwh c r r t ned mech n a al y -ytth ma erial-Thistp enqm n m r fer ed Q s the draining effect, may lead ttopirregulardyeings' that arewnottresistant tQr l b ng -l t I lf'plvl @12 H211hfliflildjbfifin propos eduto re edy these" disad vantageousproperties-of the-tknowntlevelling agents by the addition of specialcombination;preparations :for example gmixturesof paraffin oil, emulsifiers-and scumming a g ents but lthetusefof SfUfCh products; rendersthe dyeing operatiomcornplicatedtand costly. e

Finally, it; is lalsoj known to use as ,wo ol levelling agents compoundsobtained: @by ;reactingl,estjer ifiable pqlyglycol compounds whose;molecule 1 contains t at leastroneabasici nitrogematom, alipophilieresidue and a; polyglycolychainl of at least 41ethoxy; groups,- Withsuhphatizingu-or; phosphat izing agents anditolquaternatez at leastone;tertiary/nitrogen atom,withdimethylsulphate. The known compoundsofthisncomposition, "arei hows ever; only;Dccasionally suitable: as:levelling (agents for woolddy estuffsn andwin addition they; deformcross- 1" 'f'il M: ':l& w t i i mUnexpec'tedlyit has been'ufoundthatgthegnew polygly- Col:c or npounfds of .thisiinv.jention arelfreefrom ,all the aforesaidldisadvantages of the.- know levelling agents indyeing wool; this means thatzthere are now for the first timelavailable(levelling-agents; which, on: simple additioni-tonthe-tdyebathsatisfy all practical requirements and render unnecessary theadditionaluse of auxil'aries thatz nrendergthe: dyeing operation,clomplicatedqand ii/Accordingly; the -presen'tw invention includes also'a pnocejsscfor dyein'g nitrogenous fibres suitable :forudye:

'odsfiTheremay be used the conventional wool dyestuffs that contain atleast one acid group'imparting solubility in water, that is to say acarboxylic acid group or sulphonic acid group that does not participate'in the fo'rmationofla metal complex; for: example acid; ,wool dyestuffs"ifreea from metal bound in awcomplex "union, also rchromium complexcompounds containing sulphonicxaoidrgroupsmf monoazo'dyestuffsin which latom of ch'romium is bound'in complex union with il water-solublereaetive dyestuffsn 1 it v i mThe preferably. used :reactivie dyestuffsmust contain atleast one. group capable .oftre'acting with thenitrogenous fibre, or a reactive'substituent. ln other respec ts theymay belong to a wide variety of types of dyestuffs, for example thestilbene dyestuffs, perinone dyestuffs, peridicarboxylic acid imidedyestuffs, nitro dyestuffs, triphenylmethane dyestuffs, phthalocyaninesand above all the acid anthraquinone and azo dyestuffs, includingmetal-free, metallizable and metalliferous monoazo and polyazo dyestuffswhich contain groups or a substitutent capable of reacting with thenitrogenous fibres. The dyestuffs contain at least one, as a rule two ormore, acid groups imparting solubility in water. As a rule, particularlyvaluable results are obtained with dyestuffs that contain threesulphonic acid groups.

From among the above-mentioned reactive groups or substituents of thereactive dyestuffs there may be mentioned, for example, the ethylenimidegroups, epoxide groups, the vinyl grouping in a vinylsulphone group orin the acrylic acid residue, and above all those labile substituentswhich are easy to eliminate with entrain ment of the bondelectron pair.

As labile substituents eliminable with entrainment of the bond electronpair there may be mentioned, for example, aliphatically bound phosphoricor sulphuric acid ester groups, sulphonic acid fluoride groups,aliphatically bound sulphonyloxy groups and above all halogen atoms,especially a mobile chlorine atom. These labile substitutents areadvantageously in position y or B of an aliphatic residue which is boundwith the dyestuff molecule either directly or through an amino, sulphoneor sulphonamide group. In the reactive dyestuffs that contain as labilesubstituents halogen atoms, these mobile halogen atoms may also becontained in an aliphatic acyl residue (for example in the B-position ofa propionyl residue) or preferably in a heterocyclic system, and in thelast-mentioned case there are suitable dyestuffs containing amonohalogenated heterocyclic system, for example a monochlorinated1,3,5-triazine residue, such as the 1,3,5- triazine residue of theformula C l X (where X represents an alkyl, aryl, aralkyl, alkylmercaptoor arylmercapto residue, or preferably a possibly substituted aminogroup or a preferably substituted hydroxyl group) as well as dyestuffscontaining a dichlorotriazine residue or dyestuffs containing adichloropyrimidine residue. Further suitable are reactive dyestuffscontaining a-bromoor a-chloroacrylamino groups with 2,3-dichloroquinoxylinoyl, dihalogenophthalazine, dichloropyridazone,2'chlorothiazole, propionylsulphone residues or residues of the formulaeCH -NH-OC- alkyl-dihalogen, -CH NH-OC-alkenyl-halogen or -NH- SO -CH -CH-O-SO H.

The reactive dyestuffs of the kind defined above are accessible by knownmethods, for example from dyestuff components containing the said labilesubstituents or a residue containing such labile substituents, byincorporation in the dyestuff molecule by a known method after thedyestuff has been manufactured. Thus, on reaction of azo oranthraquinone dyestuffs containing a reactive hydroxyl, mercapto orabove all amino groups, with, for example chloroacetylchloride, withB-bromoor B-chloropropionylchloride or chloropropionic acid anhydride,with cyanuric chloride or with a primary condensation product fromcyanuric chloride containing two chlorine atoms and instead of the thirdchlorine atom of cyanuric chloride or organic residue, there areobtained reactive dyestuffs that further contain a mobile chlorine atom.Such reactive dyestuffs, which contain a sulphonylated hydroxyl group,can be prepared, for example, by reacting 1 mol of a dyestuff whichcontains a hydroxyalkyl group (for example a sulphonicacid-N-hydroxyalkylamide group or a B-hydroxyalkylsulphonic acid) withat least one mol of an organic sulphenylhalide, for example paratoluenesulphonyl chloride, benzenesulphonyl chloride or ethanesulphonylchloride, or with concentrated sulphuric acid or with chlorosulphonicacid in a manner such that the hydroxy group is acylated.

The amounts of the ingredients of the aqueous dyebaths to be used in thepresent dyeing process may vary within relatively wide limits. Theamount of dyestuff depends, of course, on the desired tinctorialstrength. It is advantageous to use 0.25 to 6 percent, preferably 0.5 to3 percent, of the nitrogeneous compound referred to the weight of thewool to be dyed.

However, even in the case of light shades, for which less than 1 percentdyestuff referred to the weight of the fibre is used, the amount of thenitrogen substance should be at least 0.25 percent, likewise referred tothe weight of the fibre.

Furthermore, it is advantageous to dye in an acid bath so that thedyebath should have a pH within the range from about 2 to 6. This pHvalue may be adjusted by adding acetic acid, or if desired formic orsulphuric acid. It is advantageous to add to the dyebath also sodiumsulphate.

As is usual in dyeing nitrogenous fibres, especially wool, dyeing iscarried out at an elevated temperature; it is advantageous to start theactual dyeing process at about 50 to 80C. then heating the bath to to Cor to the boil, and continuing and completing the dyeing process at thistemperature.

To ensure that the effect of the nitrogenous compound is achieved fromthe start, it is advantageous to immerse the material to be dyed in thedyebath which contains acid, if desired sodium sulphate, as well as theauxiliary, that is to say the nitrogenous compound at room temperatureor at an at most slightly higher temperature, then to heat the dyebathand to add the dyestuff in the form of an aqueous solution at anelevated temperature, for example at 50 to 80C Unless otherwiseindicated, parts and percentages in the following Examples are byweight.

EXAMPLE I 580 Parts (1 mol) of the adduct from 1 mol of a commercialfatty amine (tallow fatty amine; containing 35 percent ofhexadecylamine, 25 percent of octadecylamine and 45 percent ofoctadecenylamine) with about 7 mols of ethylene oxide are heated to 60to 65C.

In the course of 30 minutes 145 parts of chloroacetamide, then within 15minutes 107 parts of urea and within 30 minutes 107 parts ofamidosulphonic acid are stirred in. The batch is heated within one hourto C,

stirred for 6 hours at 95 to 98C and dissolved in 600 parts of water, toyield a solution of about 50 percent Preparation A) which contains thecompound (CH CHJH SO NH (n+m) average 7 in which R represents thehydrocarbon residue of tallow fatty amine.

EXAMPLE 2 580 Parts (1 mol) of the adduct from one mol of a commercialfatty amine (containing 35 percent of hex adecylamine, 25 percent ofoctadecylamine and 45 percent of octadecenylamine) and about 7 mols ofethylene oxide are heated to 90C.

In the course of about 15 minutes 120 parts of ethylenechlorohydrin arestirred in and the whole is quaternated for 24 hours at 120C. At about60C there are then added 107 parts of urea and 107 parts ofamidosulphonic acid, and the batch is heated for another 6 hours atabout 95C. The contents of the reactor are dissolved in 600 parts ofwater, to yield a 50 percent solution Preparation B) which contains theammonium salt of the monosulphuric acid ester of the compound in which Rrepresents the hydrocarbon residue of tallow fatty amine.

EXAMPLE 3 368 Parts (1 mol) of a commercial alkylpropylenediamine of theformula R-HN-(CH -NH where R is the hydrocarbon residue corresponding tosoybean fatty amine, are reacted with 352 parts (8 mols) of ethyleneoxide.

144 Parts one fifth of the total amount obtained) of this adduct areheated to 60 to 65C. 50 Parts of chloroacetamide are stirred in within30 minutes, and the whole is heated for 10 hours at 95 to 100C, thencooled to 60C, and within minutes mixed with 22.4 parts of urea and thenwithin 30 minutes with 22.4 parts of amidosulphonic acid. The whole isthen heated for 6 hours at 95 to 98C and dissolved in 290 parts ofwater, to yield a 40 percent solution Preparation C) which contains theammonium salt of the acid monosulphuric acid ester of the compoundCHZCONH-L, crncorvn in which R represents the residue of soybean fattyamine.

EXAMPLE 4 The procedure is as described in Example 1, except that thechloroacetamide is replaced by an equal quantity 145 parts) ofepichlorohydrin, to yield an approximately 50 percent solutionPreparation D) which contains the ammonium salt of the monosulphuricacid ester of the compound of the formula (n+m) average 7 where Rrepresents the hydrocarbon residue of tallow fatty amine.

EXAMPLE 5 93.5 Parts (1 mol) of chloroacetamide is stirred at 60 to 65Cinto 500 parts of the adduct described in the first paragraph ofExample 1. and the whole is treated for 24 hours on a boiling waterbath.

At 60 to 65C there are then added 214 parts of urea and 214 parts ofamidosulphonic acid and the mixture is esterified for 6 hours on aboiling waterbath. The reaction mixture is then dissolved in 440 partsof water, to form a solution of approximately 50 percent strengthPreparation E) which contains the compound in which R represents theresidue of tallow fatty amine.

EXAMPLE 6 R (n+m) average 4 where R represents the residue of tallowfatty amine.

EXAMPLE 7 The procedure is as described in Example 6, except that 795parts (1 mol) of the adduct from tallow fatty amine and 11 mols ofethylene oxide are used. After quaternation and esterification the batchis dissolved in 1220 parts of water, to form an approximately 50 percentsolution Preparation G) containing the compound (n+m) average l 1 whereR represents the residue of tallow fatty amine.

EXAMPLE 8 665 Parts (1 mol) of an adduct from one mol of a commercialfatty amine (containing about percent of stearylamine, 55 percent ofarachidylamine and 35 percent of behenylamine) and 8 mols of ethyleneoxide are quaternated with 145 parts of chloroacetamide for 12 hours at100 to 105C. At 80C 107 parts of urea and 214 parts of amidosulphonicacid are gradually added; the whole is esterified for 6 hours at 100 to105C and dissolved in 760 parts of water, to form an approximately 50percent paste Preparation H) containing the compound R (n +m) average 8where R represents the residue of tallow fatty amine.

EXAMPLE 9 The procedure is as described in Example 1, except that thechloroacetamide is replaced by 196 parts of epibromohydrin. After thereaction with epibromohydrin and amidosulphonic acid 635 parts of waterare added, to form an approximately 50 percent solution Preparation 1)containing the ammonium salt of the monosulphuric acid ester of thecompound (n-l-m) average 7 where R represents the hydrocarbon residue oftallow fatty amine.

EXAMPLE 10 The procedure is as described in Example 2, except that theethylenechlorohydrin is replaced by 188 parts of ethylenebromohydrin andthe mixture is quarternated for 24 hours at 105 to 110C, to form anapproximately 50 percent solution Preparation K) containing the ammoniumsalt of the acid monosulphuric acid ester of the compound (n+m) average7 where R represents the hydrocarbon residue of tallow fatty amine.

EXAMPLE 11 10 suction-filtered, and the volatile constituents areexpelled from the filtrate by distillation under vacuum. The residue isdissolved in 820 parts of water, to form a product Preparation L) whichcontains about 50 percent of the compound (n+ml average 7 where Rrepresents the residue of tallow fatty amine.

EXAMPLE 12 580 Parts (1 mol) of the adduct described in the firstparagraph of Example 1"are quaternated with 122 parts of chloroacetamidefor 24 hours at 95 to 100C. At C 108 parts of maleic anhydride are addedwithin 30 minutes and the batch is heated for 30 minutes at 100C andthen for 30 minutes at 120C. 780 Parts of water and 200 parts of sodiumsulphite are then added at to C, and the batch is heated for anotherhour at 95 to 100C, to form a paste Preparation M) which contains about50 percent of the compound where R represents the residue of tallowfatty amine.

EXAMPLE 13 u Nan on I HO-CH -CH -NH within 45 minutes the temperature israised to the boil and dyeing is performed for 1 hour at the boil. Thewhole is then cooled, the yarn rinsed in cold water and dried, tofurnish a level red dyeing.

By virtue of the special properties of Preparation A there occur duringthe dyeing operation no deformations of the material packing, no channelformation, no scum and no floating of the yarn being dyed. Fine worstedyarns do not undergo felting.

The adduct Preparation A+ reactive dyestuff always remains water-solubleso that no precipitations occur nor do dehydration phenomena (theso-called draining effect) intervene.

Similar results areobtained with the dyestuffs of the followingformulae:

7 80321 as HZC-G c art-Om N (rod) HOS 5 w 0 r c N N (orange) i --SO l-IN coo Eg Q o n==c (blue) EXAMPLE 14 J 1 H @40 1! w H0 3 H0 5 within 60minutes the temperature is raised to the boil and the yarn is boiled for1 hour. The steam is then turned off, 3.2kg of ammonia of percentstrength are added, and the yarn is treated in the cooling dyebath for20 minutes, then thoroughly rinsed and in the last rinsing bathacidified with 2kg of formic acid of 85 percent strength for 10 minutes.Finally, the crosswound bobbins are dehydrated and dried. The yarn isdyed a fast, brilliant red shade.

During the dyeing process no scum forms and the cross-wound bobbins arenot deformed. No disturbance of the circulation of the dye liquor clueto channel formation occurs so that the resulting dyeing is perfectlylevel.

Advantageous results are also obtained when in this Example PreparationB is replaced by an equal quantity of Preparation A (Example 1), C(Example 3), D (Example 4) or E (Example 5) or the dyestuff shown inExample 6.

EXAMPLE 15 4 Pieces of wool fabric, totalling l00kg, are wetted in awinch vat in 4000 liters of water at 50C. The following additions arethen made: 5kg of sulphuric acid of98 percent strength, 10kg ofcrystalline sodium sulphate, 2kg of Preparation C of Example 3 and0.46kg of the l:l-chromium complex of the dyestuff of the formula no son o 3 110 s -n a Hts:

(blue) 0.40kg of the lzl-chromium complex of the dyestuff of the formulaand 0.2lkg of the lzl-chromium complex of the dyestuff of the formula(yellow) The whole is heated to the boil within 45 minutes and thenboiled for 1 hour, then slowly cooled by running in cold water,thoroughly rinsed, centrifuged and dried. The woollen pieces are dyed agrey shade of good surface and fibre levelness. During the dyeing thepieces do not tend to float but always remain inside the dye liquor(with the exception, of course, of the path over the dye winch).Furthermore, no precipitations occur.

EXAMPLE 16 100 Kilograms of loose wool (flocks) are wetted in 2000liters of water at 50C in a circulation vat. The following additions arethen made: 2kg of glacial acetic acid, 10kg of crystalline sodiumsulphate, 2kg of Preparation D of Example 4, and 1kg of the bluedyestuff of the formula s mic o a b it 3 it 5: Er

The whole is heated within 60 minutes to the boil and then boiled for 60minutes, and the wool is then rinsed and dried. The wool is dyed a levelturquoise shade of good fastness properties. During the dyeing nodisturbing scum forms. Since by virtue of the special behaviour ofPreparation D no channels are formed in the material block, theresulting levelness is excellent.

EXAMPLE 17 A machine for dyeing cross-wound bobbins is packed with 100kgof cross-wound bobbins of pure wool yarn. in the dye liquor containerassociated with this machine a dye liquor is prepared from 1200 litersof water at 50C kg of sodium sulphate 2 kg of glacial acetic acid 1 kgof the dyestuff of the formula shown in Example 16 and finally 1 kg ofPreparation D of Example 4 is added.

This dye liquor is pumped into the machine for dyeing cross-woundbobbins mentioned above, heated within 40 minutes to the boil and thewhole is boiled for 1 hour; the yarn is then thoroughly rinsed anddried. It is dyed a level turquoise shade of good fastness properties.During the dyeing operation the cross-wound bobbins are not deformed andno channels form in the material.

EXAMPLE 18 100 Kilograms of wool yarn in the form of crosswound bobbinsare wetted in 2000 liters of water at 50C for minutes in a machine fordyeing crosswound bobbins. The following additions are then made: 6kg ofsulphuric acid of 96 percent strength, 10kg of crystalline sodiumsulphate, 1kg of Preparation A of Example 1 and 1kg of the red dyestuffof the formula 1:1-chromium complex.

Within 30 minutes the temperature is raised to 80C and the yarn is dyedat this temperature for 1 hour, then rinsed and buffered with sodiumacetate. The wool yarn is dyed a level, fast, red shade. The crosswoundbobbins are not deformed.

Instead of Preparation A there may be used Preparation F or L. Withequally good results the dyestuffs of the following formula may be used:

S0 Na H0 S OHH 91 I NIN-C\ i IN-chromium complex Cl H (red) H I--N=N*Kc//,N 0 11 6H g 1:1-chromium complex 14 H Ht? O HH HO S- N Nag1:1-chromium complex (blue) H 1106 OH II I N=N-C N (orange) 1x1-ehromiumcomplex OH H -O I I HO 3 N I: N 3 RC4! I CH (P 1:l-chromium complex B noso H M l H 3 KW so H 3 (blue) 1 1-chromium complex EXAMPLE 19 100Kilograms of wool yarn in the form of crosswound bobbins are wetted in1500 liters of water at 50C for 10 minutes in a machine for dyeingcrosswound bobbins. Then the following additions are made: 5.5kg ofsulphuric acid of 96 percent strength, 10kg of crystalline sodiumsulphate, 1kg of Preparation G of Example 7 and 2kg of one of thedyestuffs shown in Example 18.

The temperature is raised to the boil within 50 minutes and the yarn isboiled for 1 hour, then thoroughly rinsed. The wool yarn is dyed a fast,level, blue shade. The dyeing operation does not deform the cross-woundbobbins. Instead of Preparation G there may be used Preparation H or M.

EXAMPLE 20 100 Kilograms of wool yarn are pre-wetted in 2,000 liters ofwater with addition of 2kg of acetic acid of percent strength and 1kg ofPreparation A for 10 minutes in a hank dyeing machine, whereupon 1kg ofthe dyestuff of the formula I cn o Oo H SO [-1 H 5 3 (scarlet) is added.The temperature is raised within minutes to 70C and the yarn is dyed for60 minutes at this temperature, then rinsed and dyed. The wool yarn isdyed a level, fast red shade. The dyestuff used above may be replaced byone of the following dyestuffs:

0\C N Ho sOu=N-" (y 110w) (3H (red) EXAMPLE 21 100 Kilograms of woolyarn are pre-wetted in 2000 liters of water at 50C with addition of 2kgof acetic acid of 80 percent strength, 10kg of crystalline sodiumsulphate and 2kg of Preparation J for 10 minutes in a single-tier hankdyeing machine, whereupon lkg of the reactive dyestuff of the formula uc-cocmi I Br 80 3 (red) is added. The whole is raised to the boil withinminutes and boiled for one hour. The 3kg of ammonia of 25 percentstrength are added, the yarn is treated for 20 minutes in thecooling-off dyebath, rinsed and in the last rinse acidified with lkg offormic acid of 85 percent strength.

A fast, vivid and level red shade is obtained. lnstead of the dyestuffused above there may be used the following dyestuff:

(red) HO soon on -so 3 no N I N-m (red) 11. x g mmiccc-ca (angelH2C=C0CHH 3 is I Br 021 (red) 3 2 H ZNHCOCH CH2 Br Br 003}! pa F3 803B(blue) Q OQL H c H0 50 B I ir Br Br I HO Br EXAMPLE 22 100 Kilograms ofwool yarn cross-wound bobbins are pre-wetted in 2000 litres of waterwith addition of 2kg of Preparation K, 2kg of acetic acid of 80 percentstrength and kg of crystalline sodium sulphate for 10 minutes at 50C ina machine for dyeing cross-wound bobbins. Then 2kg of the dyestuff ofthe formula 5 no (JD-g} N 6-8 n o/ H038" HO3S so ria I C l are added.The whole is heated to the boil within 30 minutes and boiled for onehour, then rinsed and dried. The wool wherein R is a linear aliphatichydrocarbon radical selected from the group consisting of alkyl andalkenyl radicals with 12 to 24 carbon atoms,

X is a radical selected from the group consisting of monodeshydroxypolybasic oxygen acid radical of an at least dibasic oxygen acidselected from the group consisting of sulfuric acid and succinic-suL 1:Z-chromium complex fonic acid and the alkali metal and ammonium salt ofsaid monodeshydroxy oxygen acid radical,

Hal is chloride or bromide p, q, and s are whole numbers, s is l or 2,and the sum (p+q) is 4 to 12.

(red) 2. A compound of claim 1, wherein X is a radical selected from thegroup consisting of the alkali metal and ammonium salts of themonodeshydroxy sulfuric acid radical.

3. A compound of claim 1, wherein X is an alkali metal salt of themonodeshydroxy succinic-sulfonic acid radical.

4. A compound of claim 1, wherein R is the hydrocarbon radical of tallowfatty amine, X is -SO NH R is Nl-l C(#))CH Hal is chloride, 5 is l andthe average value of p+q is about 7.

5. A compound of claim 1, wherein R is the hydrocarbon radical of tallowfatty amine, X is -SO Nl-l R is NH C(=0)CH Hal is chloride, sis 2 andthe average value of p+q is about 7.

6. A compound of claim 1, wherein R is H C- (Cl-l -CH X is -SO NH R isNH C(=0)Cl-l Hal is chloride, 5 is 2 and the average value of p+q isabout 8.

UNITED STATES PATENT OFF-ICE CERTIFICATE OF CORRECTIQN PATENT NO.5,919,285 DATED November 11 1975 INVENTOR(S) Alfred Berger, et al It iscertified that error appears in the above-identified patent arrd thatsaid Letters Patent are hereby corrected as shown below:

Claim 1 column 17, between lines 55 and 60, the left-hand portion of thestructural formula should read:

The following changes are changes which should apply to the grant only:

Column 18, line 55, "R" should read --R'-.

Claim r, line 2, "R" should read -R'-.

Claim 5, line 2, R" should read --R'-.

Claim 6, line 2, "R" should read -R'-.

Signed and Scaled this Ninth Day of November 1976 [SEAL] A nest:

RUTH C. MASON C. MARSHALL DANN Arrcsrr'nx Officer (nmmim'nnor nj'Palemsand Trademark:

1. AN AMPHOTERIC COMPOUND OF THE FORMULA
 2. A compound of claim 1,wherein X is a radical selected from the group consisting of the alkalimetal and ammonium salts of the monodeshydroxy sulfuric acid radical. 3.A compound of claim 1, wherein X is an alkali metal salt of themonodeshydroxy succinic-sulfonic acid radical.
 4. A compound of claim 1,wherein R is the hydrocarbon radical of tallow fatty amine, X is-SO3NH4, R'' is NH2C( 0)CH2-, Hal is chloride, s is 1 and the averagevalue of p+q is about
 7. 5. A compound of claim 1, wherein R is thehydrocarbon radical of tallow fatty amine, X is -SO3NH4, R'' is NH2C(0)CH2-, Hal is chloride, s is 2 and the average value Of p+q is about 7.6. A compound of claim 1, wherein R is H3C-(CH2)16 20-CH2-, X is-SO3NH4, R'' is NH2C( 0)CH2-, Hal is chloride, s is 2 and the averagevalue of p+q is about 8.